Organocatalytic Synthesis and Postpolymerization Functionalization of Allyl-Functional Poly(carbonate)s

Well-defined allyl-functional poly(carbonate)s were synthesized via the organocatalytic ring-opening polymerization of 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one using the dual 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea and (−)-sparteine catalyst system. The resulting allyl-functional poly(carbonate)s obtained showed low polydispersities and high end-group fidelity, with the versatility of the system being demonstrated by the synthesis of block copolymers and telechelic polymers. Further functionalization of homopolymers with degrees of polymerization of 11 and 100 were realized via the radical addition of thiols to the pendant allyl functional groups, resulting in a range of functional aliphatic poly(carbonate)s.